Catalytic or  photocatalytic  preparation method of parylene af4

ABSTRACT

The present invention disclosed a preparation method of parylene AF4, which provides a reactant and a reducing agent with the use of catalyst or exposure to UV light with photo-initiator, to shorten the reaction time as a result of minimized the byproduct(s) formation, and obtain high purity (&gt;99.0%) of parylene AF4 product under high concentrated reaction mixture.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.13/623,926, filed Sep. 21, 2012, which claims benefit to TaiwaneseApplication No. 101125578, filed Jul. 6, 2012, the entire contents ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a preparation method ofoctafluoro-(2,2)-paracyclophane (parylene AF4) and, more particularly,the present invention relates to a catalytic or a photocatalyticpreparation method of parylene AF4.

2. Description of Related Art

By using the vacuum pyrolysis chemical vapor deposition (CVD) method,parylene can be made into an extremely thin film which has an excellentuniformity, chemical stability and high transparency. Parylene is widelyused in the forms of coating thin film, for application on theelectrical isolation of printed circuit board, moisture protection ofsensors or medical equipment, insulating layers of electrical unit,various protective films or packing materials, and preventing corrosionof metal coatings.

Recently, due to high melting point (about 450° C.) and low dielectricconstant (about 2.2) of the fluorinated parylene polymers, such aspoly(tetraflouro-para-xylene) (parylene HT), with its structure shown informula (1), compared to the traditional parylene N, parylene C, andparylene D, it has superior anti-UV properties, aging resistance, andthermal stability.

In addition, parylene HT can be coated on various irregular substrates'surface, for example, glass, metal, resin, plastic, ceramic and paper.The products coated with parylene HT usually have excellentanti-corrosion, anti-moisture, and insulation protection performance,with the advantages of ultra-thin, transparent, and pinholes free,parylene HT can be used in electronic units, automotive industries,solar energy industries, and the low dielectric constant films ofsemiconductor industries. Currently, the coating of parylene HT isprepared via CVD process. During the CVD process, free radical monomersare produced and then polymerized into parylene HT on the surface of theobject: the method is different from the other general preparation vialiquid coating methods (such as dip-coating, spray-coating,sputter-coating, and plasma-coating). The coating process first includesthe vaporization of fluorinated parylene dimer, such as parylene AF4(formula (2)); then forming fluorinated para-xylene radicals byhigh-temperature pyrolysis; finally deposited on the coated substrate;and polymerized to poly(tetraflouro-para-xylene), which is commonlynamed parylene HT, as shown in formula (1), on the surface of the coatedobject.

The mechanism of the parylene AF4 polymerized to parylene HT via CVD isshown in formula (3).

Many synthetic methods of parylene AF4 has been published in theliterature, which mainly use 1,4-bis(chlorodifluoromethyl)benzene (CFB),shown in formula (4), to react with reducing agent Zinc (Zn) and obtainthe parylene AF4. In the previous methods, however, in order to preventthe undesired byproducts formation, the reactions were usually carriedout in highly diluted conditions, that is, large amount of solvents arenecessary in the synthetic methods, therefore, the purchase and storageof the solvent, the process of feeding and the removal of the solvent orimpurities will increase the cost of the preparation, coupled with longreaction time, more byproducts and complication of parylene AF4purification procedure, those methods are not suitable for massproductions.

Therefore, there is a need for the development of a parylene AF4(octafluoro-[2,2]-paracyclophane) preparation method characterized byhigh reactant concentration, short reaction time, low cost, lessbyproducts, easy purification, good reproducibility and stable yield.

SUMMARY OF THE INVENTION

The present invention provides a preparation method for synthesizingparylene AF4 (octafluoro-[2,2]-paracyclophane) using catalyst orphotocatalytic, which can reduce the reaction time and increase theyield of parylene AF4 by high concentrated reaction mixture.

In order to achieve the objective, the preparation method of usingcatalyst of the present invention includes: (A) providing a reactant, areducing agent, and a catalyst, wherein the reactant is at least oneselected from the group consisting of1,4-bis(chlorodifluoromethyl)benzene (CFB),1,4-bis(bromodifluoromethyl)benzene (BFB), and1,4-bis(iododifluoromethyl)benzene (IFB); the reducing agent is at leastone selected from the group consisting of zinc, nickel, lead, aluminum,copper, magnesium and tin; and the catalyst is at least one selectedfrom the group consisting of (1) an alkali metal salt, an alkali metaloxide, an alkali metal peroxide, an alkali metal hydroxide, and analkali metal amide; (2) an alkali earth metal salt, an alkali earthmetal oxide, and an alkali earth metal hydroxide; (3) a transition metalsalt, a transition metal oxide, a transition metal hydroxide, and atransition metal salt containing hydrate; (4) an amphoteric elementsalt, an amphoteric element oxide, an amphoteric element hydroxide, anamphoteric element peroxide, and an amphoteric element salt containinghydrate; (5) a non-metallic element acid, and a non-metallic elementoxide; (6) a halogen; (7) a phase transfer catalyst of quaternaryammonium salt, a phase transfer catalyst of quaternary phosphonium salt,and a phase transfer catalyst of crown ether; (B) forming a mixture byadding the reactant, the reducing agent, and the catalyst into anaprotic polar solvent; (C) heating the mixture to obtain the paryleneAF4 (octafluoro-[2,2]-paracyclophane).

The other preparation method of photocatalytic reaction of the presentinvention includes: (A) providing a reactant, and a reducing agent,wherein the reactant is at least one selected from the group consistingof 1,4-bis(chlorodifluoromethyl)benzene,1,4-bis(bromodifluoromethyl)benzene, and1,4-bis(iododifluoromethyl)benzene; the reducing agent is at least oneselected from the group consisting of zinc, nickel, lead, aluminum,copper, magnesium and tin; (B) forming a mixture by adding the reactantand the reducing agent into an aprotic polar solvent; (C) providing anUV light source and heating the mixture to obtain the parylene AF4(octafluoro-[2,2]-paracyclophane). Wherein, the step (B) of the abovefurther comprises at least a photoinitiator, which is at least oneselected from the group consisting of diazo compounds, peroxides,anthraquinones, phosphine oxides, and ketones.

According to the preparation method of the present invention, thereactant may be single component of CFB, BFB, or IFB; or two-componentmixture of CFB and BFB, CFB and IFB, or BFB and IFB; or three-componentmixture of CFB, BFB and IFB.

According to the preparation method of the present invention, wherein instep (B), the electrochemical potential of the reducing agent must be ofthe value between 0.45˜2.5 eV, and the reducing agent is at least oneselected from the group consisting of zinc, nickel, lead, aluminum,copper, magnesium and tin, wherein zinc is preferable. The weight ratioof the reducing agent to the reactant is 1:1˜5, wherein 1:1.23.0 ispreferable.

In the method according to the present invention, the aprotic polarsolvent in step (B) is at least one selected from the group consistingof N,N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO),dimethylformamide (DMF), tetrahydrofurane (THF), N-methylpyrrolidone(NMP), and acetonitrile (AN), wherein DMAC is preferable. The weightratio of the reactant to the solvent is 1:1˜30, wherein 1:1.5˜10 ispreferable.

The method of using catalyst according to the present invention, whereinthe catalyst used in step (B) is at least one selected from the groupconsisting of (1) an alkali metal salt, an alkali metal oxide, an alkalimetal peroxide, an alkali metal hydroxide, an alkali metal amide; (2) analkali earth metal salt, an alkali earth metal oxide, an alkali earthmetal hydroxide; (3) a transition metal salt, a transition metal oxide,a transition metal hydroxide, a transition metal salt containinghydrate; (4) an amphoteric element salt, an amphoteric element oxide, anamphoteric element hydroxide, an amphoteric element peroxide, anamphoteric element salt containing hydrate; (5) a non-metallic elementacid, a non-metallic element oxide; (6) a halogen; (7) a phase transfercatalyst of quaternary ammonium salt, a phase transfer catalyst ofquaternary phosphonium salt, and a phase transfer catalyst of crownether; wherein (1) the alkali metal salt are preferred to be alkalimetal halide salt, alkali metal sulfate, alkali metal carbonate, alkalimetal acetate, alkali metal nitrate, alkali metal amine salt, alkalimetal organic salt, alkali metal phosphite, alkali metal persulfate, andalkali metal oxalate, wherein CF₃COOLi, LiNH₂, KH₂PO₃, KF, KCl, KBr, KI,CH₃COOK, K₂SO₄, potassium hydrogen phthalate (KHP), potassiumtert-butoxide, Na₂SO₄, K₂S₂O₈, K₂CO₃, potassium acrylate, NaCl, NaI,Na₂CO₃, NaNH₂, CH₃COONa, C₂H₅ONa, C₆H₅COONa, CH₃ONa, C₆H₄(OH)COONa,sodium oxalate, and CsF are more preferable, wherein CF₃COOLi, LiNH₂,KH₂PO₃, KF, KCl, KBr, KI, K₂SO₄, K₂S₂O₈, potassium acrylate, NaCl, NaI,Na₂SO₄, NaNH₂, CH₃COONa, CH₃ONa, sodium oxalate, and Na₂CO₃ are mostpreferable; the alkali metal oxide is preferred to be Na₂O; and thealkali metal peroxide is preferred to be Na₂O₂; the alkali metalhydroxide are preferred to be LiOH, and NaOH; wherein NaOH is morepreferable; the alkali metal amide is preferred to be potassiumphthalimide; (2) the alkali earth metal salt are preferred to be alkaliearth metal halide salt, alkali earth metal sulfate, alkali earth metalcarbonate, and alkali earth metal nitrate, wherein CaCl₂, CaCO₃, CaSO₄,MgCl₂, MgSO₄, MgCO₃, Ba(NO₃)₂ and BaCl₂ are more preferable, whereinCaCl₂, CaCO₃, MgCl₂, MgSO₄, MgCO₃, and BaCl₂ are most preferable; thealkali earth metal oxide are preferred to be MgO and CaO; the alkaliearth metal hydroxide is preferred to be Ca(OH)₂; (3) the transitionmetal salt are preferred to be transition metal halide salt, transitionmetal acetate, transition metal sulfate, transition metal nitrate, andtransition metal carbonate, wherein Ag₂SO₄, NiCl₂, NiCO₃, CuI₂, ZnSO₄,and ZnCl₂ are more preferable, wherein CuI₂ is most preferable; thetransition metal oxide is preferred to be ZnO; the transition metal saltcontaining hydrate are preferred to be Zn(NO₃)₂.6H₂O, Zn(CH₃COO)₂.2H₂O,Fe(NO₃)₃.9H₂O, FeCl₃.6H₂O, MnSO₄.H₂O, CuCl₂.2H₂O, Cu(NO₃)₂.2.5H₂O, andCoCl₂.6H₂O, wherein Zn(NO₃)₂.6H₂O, MnSO₄.H₂O, and Cu(NO₃)₂.2.5H₂O aremore preferable; (4) the amphoteric element salt are preferred to beamphoteric element halide salt, amphoteric element sulfate, andamphoteric element nitrate, wherein PbCl₂, Pb(NO₃)₂, and SnCl₂ are morepreferable; the amphoteric element oxide are preferred to be PbO andPb₃O₄; the amphoteric element hydroxide is preferred to be Al(OH)₃; theamphoteric element salt containing hydrate are preferred to bePb(CH₃COO)₂.3H₂O and Al(NO₃)₃.9H₂O, wherein Pb(CH₃COO)₂. 3H₂O is morepreferable; (5) the non-metallic element acid is preferred to be boricacid; the non-metallic element oxide is preferred to be P₂O₅; (6) thehalogen are preferred to be bromine (Br₂) and iodine (I₂); (7) the phasetransfer catalyst of quaternary ammonium salt are preferred to betetramethyl ammonium chloride (PTC-A₁), phenyl trimethyl ammoniumchloride (PTC-A₂), and benzyl triethyl ammonium chloride (PTC-A₃),wherein PTC-A₁ and PTC-A₂ are more preferable; the phase transfercatalyst of quaternary phosphonium salt are preferred to be tetraphenylphosphonium bromide (PTC-B₁) and methyl triphenyl phosphonium bromide(PTC-B₂), wherein PTC-B₁ is more preferable; and the phase transfercatalyst of crown ether are preferred to be 18-crown-6-ether,12-crown-4-ether, and 15-crown-5-ether, wherein 18-crown-6-ether is morepreferable. The weight ratio of catalyst to reactant is 1:10˜500. Inorder to shorten the reaction time, the dimerization can be acceleratedby adding catalyst and also decreasing the undesired byproductsformation.

The method according to the present invention, wherein in step (C), thereaction temperature is 50˜250° C., 80˜200° C. is preferred, and100˜135° C. is more preferable.

The method of using catalyst according to the present invention, whereinin step (C), the reaction time is 1˜24 hour, and 1˜12 hour ispreferable.

In the method of photocatalytic reaction according to the presentinvention, step (B) further comprises a photo-initiator, and thephoto-initiator is at least one selected from the group consisting ofdiazo compounds such as azobisisobutyronitrile (AIBN); peroxides such asbenzoyl peroxide (BPO); anthraquinones such as 2-ethylanthraquinone(EAQ); phosphine oxides such asdiphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (DTBPO); and ketonessuch as 1-hydroxy-cyclohexyl phenyl ketone (HCPK),2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP), benzyl-α,α-dimethylketal (BDK) and2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (MPMPO),wherein the weight ratio of the photo-initiator to the reactant is1:10˜100, and 1:30˜60 is more preferable.

The method of preparing parylene AF4 of the present invention, by addingat least a reactant selected from the group of CFB, BFB, and IFB into asmall amount of solvent combined with a reducing agent to form a highlyconcentrated reaction mixture, catalyzed by adding catalyst orphotocatalytic reaction with photo-initiator, and accelerated thereaction by heating to obtain parylene AF4. The capacity of parylene AF4production is significantly increased by the high concentrated reactionmixture, therefore, the large scale of parylene AF4 manufacture promisesgreat commercial advantages.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Embodiment 1

This embodiment involves providing a 250 ml three-necked bottle andpurging with nitrogen, then adding 75 ml of DMAC solvent, 15.68 g (0.24mol) of reducing agent zinc powder, and 0.21 g (3.5 mmol) of catalystKF, stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactantCFB is added dropwise to the reaction bottle, and the reactiontemperature is gradually increased to 135° C., the feeding time is about2 hours and the reaction is continued for 3 hours. The crude product isfiltered and washed by DMAC. The double bond-containing byproduct infiltrate is oxidized by potassium permanganate, and the filtrate isconcentrated and water is added to the resulting crude solid in order toremove the inorganic substances. The crude solid obtained fromfiltration and recrystallized in chloroform (CHCl₃) to obtain 8.43 g ofpure parylene AF4 (purity 99.5%, yield 40.28%). The parylene AF4 productis confirmed by analysis: the molecular weight of 352.0 g/mol isconfirmed by GC/MS analysis, H¹NMR is δ 7.1 ppm (s), and F¹⁹ NMR is δ−118.0 ppm (s).

Embodiment 2

In this embodiment of the present invention, a 250 ml three-neckedbottle is provided and purged with nitrogen, then 50 ml of DMAC solventis added, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g(0.6 mmol) of catalyst KI, stirred and preheated to 120° C. Then themixture of 14.82 g (0.06 mol) of reactant CFB and 1.95 g (0.006 mol) ofreactant BFB is added dropwise to the reaction bottle, and the reactiontemperature is gradually increased to 140° C., the feeding time is about1 hour and the reaction is continued for 3 hours. The crude product ispurified and analyzed by the same methods of embodiment 1 and 3.58 g ofparylene AF4 is obtained (purity 99.63%, yield 31.0%).

Embodiment 3

Provide a 250 ml three-necked bottle and purge with nitrogen, then add150 ml of DMSO solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to 120° C.Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to131° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.34% ofpurity and 26.7% of yield.

Embodiment 4

Provide a 1000 ml three-necked bottle and purge with nitrogen, then add300 ml of DMAC solvent, 125.4 g (1.92 mol) of reducing agent zincpowder, and 1.9 g (11.4 mmol) of catalyst KI, stirred and preheated to120° C. Then 237.0 g (0.96 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to142° C., the feeding time is about 3 hours and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 77.2 g of parylene AF4 is obtained (purity99.7%, yield 45.7%).

Embodiment 5

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.2 g (3.4 mmol) of catalyst NaCl, stirred and preheated to 120° C.Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to135° C., the feeding time is about 2 hours and the reaction is continuedfor 2 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 7.9 g of parylene AF4 is obtained (purity99.52%, yield 37.44%).

Embodiment 6

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.2 g (1.4 mmol) of catalyst sodium sulfate (Na₂SO₄), stirred andpreheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is addeddropwise to the reaction bottle, and the reaction temperature isgradually increased to 134° C., the feeding time is about 2 hours andthe reaction is continued for 2 hours. The crude product is purified andanalyzed by the same methods of embodiment 1 and 7.74 g of parylene AF4is obtained (purity 99.66%, yield 36.7%).

Embodiment 7

This embodiment involves to providing a 250 ml three-necked bottle andpurging with nitrogen, then adding 50 ml of DMAC solvent, 7.84 g (0.12mol) of reducing agent zinc powder, and 0.63 g (15.8 mmol) of catalystsodium hydroxide (NaOH), stirred and preheated to 120° C. Then 14.82 g(0.06 mol) of reactant CFB is added dropwise to the reaction bottle, andthe reaction temperature is gradually increased to 130° C., the feedingtime is about 1 hour and the reaction is continued for 3 hours. Thecrude product is purified and analyzed by the same methods of embodiment1 and 3.7 g of parylene AF4 is obtained (purity 99.28%, yield 35.24%).

Embodiment 8

A 250 ml three-necked bottle is provided and purged with nitrogen, thenadded with 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agentzinc powder, and 0.10 g (2.5 mmol) of catalyst MgO, stirred andpreheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is addeddropwise to the reaction bottle, and the reaction temperature isgradually increased to 130° C., the feeding time is about 1 hour and thereaction is continued for 2 hours. The crude product is purified andanalyzed by the same methods of embodiment 1 and parylene AF4 isobtained with 99.39% of purity and 30.10% of yield.

Embodiment 9

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.20 g (1.8 mmol) of catalyst CaCl₂, stirred and preheated to 120°C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to132° C., the feeding time is about 2 hours and the reaction is continuedfor 2 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 8.36 g of parylene AF4 is obtained (purity99.45%, yield 39.81%).

Embodiment 10

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.10 g (0.59 mmol) of catalyst MnSO₄.1H₂O, stirred and preheated to120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to140° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.59% ofpurity and 31.43% of yield.

Embodiment 11

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.10 g (0.32 mmol) of catalyst CuI₂, stirred and preheated to 120°C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to140° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.37% ofpurity and 30.6% of yield.

Embodiment 12

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.20 g (2.5 mmol) of catalyst ZnO, stirred and preheated to 120° C.Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to132° C., the feeding time is about 1 hour and the reaction is continuedfor 2 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.6% ofpurity and 31.00% of yield.

Embodiment 13

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.10 g (1.3 mmol) of catalyst Al(OH)₃, stirred and preheated to 120°C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to136° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.5% ofpurity and 31.42% of yield.

Embodiment 14

This embodiment of the present invention provides a 250 ml three-neckedbottle and is purged with nitrogen, then adding 75 ml of DMAC solvent,15.68 g (0.24 mol) of reducing agent zinc powder, and 0.28 g (1.0 mmol)of catalyst PbCl₂, stirred and preheated to 120° C. Then 29.64 g (0.12mol) of reactant CFB is added dropwise to the reaction bottle, and thereaction temperature is gradually increased to 130° C., the feeding timeis about 2 hours and the reaction is continued for 2 hours. The crudeproduct is purified and analyzed by the same methods of embodiment 1 and7.6 g of parylene AF4 is obtained with 99.46% of purity and 36.2% ofyield.

Embodiment 15

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.20 g (0.53 mmol) of catalyst Pb(CH₃COO)₂.3H₂O, stirred andpreheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is addeddropwise to the reaction bottle, and the reaction temperature isgradually increased to 134° C., the feeding time is about 2 hours andthe reaction is continued for 3 hours. The crude product is purified andanalyzed by the same methods of embodiment 1 and 6.63 g of parylene AF4is obtained with 99.3% of purity and 31.4% of yield.

Embodiment 16

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.30 g (2.7 mmol) of catalyst PTC-A₁, stirred and preheated to 120°C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to136° C., the feeding time is about 2 hours and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 8.6 g of parylene AF4 is obtained with99.45% of purity and 40.76% of yield.

Embodiment 17

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.50 g (1.4 mmol) of catalyst PTC-B₂, stirred and preheated to 120°C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to140° C., the feeding time is about 2 hours and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 7.53 g of parylene AF4 is obtained with99.61% of purity and 35.7% of yield.

Embodiment 18

Provide a 250 ml three-necked bottle and purge with nitrogen, then add75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder,and 0.40 g (1.5 mmol) of catalyst 18-crown-6, stirred and preheated to120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to136° C., the feeding time is about 2 hours and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 8.04 g of parylene AF4 is obtained with99.72% of purity and 38.1% of yield.

Embodiment 19

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.30 g (13 mmol) of catalyst LiNH₂, stirred and preheated to 120° C.Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to136° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.41% ofpurity and 40.5% of yield.

Embodiment 20

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.30 g (12.5 mmol) of catalyst LiOH, stirred and preheated to 120°C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to136° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.52% ofpurity and 29.8% of yield.

Embodiments 21˜100

The preparation methods, reactants, reducing agents, catalysts, solventsand the dosages, reaction temperature, reaction time and the yields ofparylene AF4 of embodiments 21˜100 are shown in table 1.

Embodiment 101

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent and 7.84 g (0.12 mol) of reducing agent zincpowder, and exposed to UV light, stirred and preheated to 120° C. Then14.82 g (0.06 mol) of reactant CFB is added dropwise to the reactionbottle, and the reaction temperature is gradually increased to 134° C.,the feeding time is about 1 hour and the reaction is continued for 20hours. The crude product is purified and analyzed by the same methods ofembodiment 1 and parylene AF4 is obtained with 99.23% of purity and33.9% of yield.

Embodiment 102

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder,and 0.30 g (1.83 mmol) of photo-initiator AIBN and then exposed to UVlight, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) ofreactant CFB is added dropwise to the reaction bottle, and the reactiontemperature is gradually increased to 132° C., the feeding time is about1 hour and the reaction is continued for 3 hours. The crude product ispurified and analyzed by the same methods of embodiment 1 and paryleneAF4 is obtained with 99.31% of purity and 33.3% of yield.

Embodiments 103˜115

The preparation methods of embodiments 103˜115 are the same asembodiment 102, and their reactants, reducing agents, photo-initiators,solvents and the dosages, reaction temperature, reaction time and theyields of parylene AF4 of embodiments 103˜115 are shown in table 2.

Comparative Example 1

Provide a 250 ml three-necked bottle and purge with nitrogen, then add100 ml of DMAC solvent, and 31.36 g (0.48 mol) of reducing agent zincpowder, stirred and preheated to 120° C. Then 59.28 g (0.24 mol) ofreactant CFB is added dropwise to the reaction bottle, and the reactiontemperature is gradually increased to 130° C., the feeding time is about2 hours and the reaction is continued for 26 hours. The crude product ispurified and analyzed by the same methods of embodiment 1 and 14.50 g ofparylene AF4 is obtained with 99.33% of purity and 34.5% of yield.

Comparative Example 2

Provide a 250 ml three-necked bottle and purge with nitrogen, then add50 ml of DMAC solvent, 3.24 g (0.12 mol) of reducing agent aluminumpowder, and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to138° C., the feeding time is about 1 hour and the reaction is continuedfor 3 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and parylene AF4 is obtained with 99.45% ofpurity and 11.8% of yield.

Comparative Example 3

A 250 ml three-necked bottle is provided and purged with nitrogen, thenadding 150 ml of AN solvent, 7.84 g (0.12 mol) of reducing agent zincpowder, and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to80° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to thereaction bottle, and the reaction temperature is gradually increased to82.5° C., the feeding time is about 1 hour and the reaction is continuedfor 20 hours. The crude product is purified and analyzed by the samemethods of embodiment 1 and 1.06 g of parylene AF4 is obtained with99.64% of purity and 10.05% of yield.

Comparative Example 4

Provide a 250 ml three-necked bottle and purge with nitrogen, then add100 ml of DMAC solvent, and 15.68 g (0.24 mol) of reducing agent Zincpowder, and exposed to UV light, stirred and preheated to 120° C. Then29.64 g (0.12 mol) of reactant CFB is added dropwise to the reactionbottle, and the reaction temperature is gradually increased to 130° C.,the feeding time is about 2 hour and the reaction is continued for 20hours. The crude product is purified and analyzed by the same methods ofembodiment 1 and parylene AF4 is obtained with 99.68% of purity and35.7% of yield.

TABLE 1 The parylene AF4 preparation enhanced by catalyst.

Reaction Parylene Reducing Solvent temperature Reaction AF4 Reactant (R)agent (RA) Catalyst (X) (S) (° C.) time (hr) yield Embodiment (g/mol)(g/mol) (g/mmol) (ml) Initial/End Feed/End (%) 1 CFB Zn KF DMAC 120/1352/3 40.28 29.64/0.12 15.68/0.24 0.21/3.5 75 2 CFB Zn KI DMAC 120/140 1/331.0 14.82/0.06 7.84/0.12 0.1/0.6 50 BFB 1.95/0.006 3 CFB Zn KI DMSO120/131 1/3 26.7 14.82/0.06 7.84/0.12 0.1/0.6 150  4 CFB Zn KI DMAC120/142 3/3 45.7 237.0/0.96 125.4/1.92 1.9/11.4 300  5 CFB Zn NaCl DMAC120/135 2/2 37.44 29.64/0.12 15.68/0.24 0.2/3.4 75 6 CFB Zn Na₂SO₄ DMAC120/134 2/2 36.7 29.64/0.12 15.68/0.24 0.2/1.4 75 7 CFB Zn NaOH DMAC120/130 1/3 35.24 14.82/0.06 7.84/0.12 0.63/15.8 50 8 CFB Zn MgO DMAC120/130 1/2 30.1 14.82/0.06 7.84/0.12 0.1/2.5 50 9 CFB Zn CaCl₂ DMAC120/132 2/2 39.81 29.64/0.12 15.68/0.24 0.2/1.8 75 10 CFB Zn MnSO₄•1H₂ODMAC 120/140 1/3 31.43 14.82/0.06 7.84/0.12 0.1/0.59 50 11 CFB Zn CuI₂DMAC 120/140 1/3 30.6 14.82/0.06 7.84/0.12 0.1/0.32 50 12 CFB Zn ZnODMAC 120/132 1/2 31.0 14.82/0.06 7.84/0.12 0.2/2.5 50 13 CFB Zn Al(OH)₃DMAC 120/136 1/3 31.42 14.82/0.06 7.84/0.12 0.1/1.3 50 14 CFB Zn PbCl₂DMAC 120/130 2/2 36.2 29.64/0.12 15.68/0.24 0.28/1.0 75 15 CFB ZnPb(CH₃COO)₂•3H₂O DMAC 120/134 2/3 31.4 29.64/0.12 15.68/0.24 0.2/0.53 7516 CFB Zn PTC-A₁ DMAC 120/136 2/3 40.76 29.64/0.12 15.68/0.24 0.3/2.7 7517 CFB Zn PTC-B₂ DMAC 120/140 2/3 35.7 29.64/0.12 15.68/0.24 0.5/1.4 7518 CFB Zn 18-crown-6 DMAC 120/136 2/3 38.1 29.64/0.12 15.68/0.24 0.4/1.575 19 CFB Zn LiNH₂ DMAC 120/136 1/3 40.5 14.82/0.06 7.84/0.12 0.3/13 5020 CFB Zn LiOH DMAC 120/136 1/3 29.8 14.82/0.06 7.84/0.12 0.3/12.5 50 21CFB Zn CF₃CO₂Li DMAC 120/136 1/3 33.7 14.82/0.06 7.84/0.12 0.3/2.5 50 22CFB Zn KF DMAC 120/132 2/2 37.91 29.64/0.12 15.68/0.24 0.3/5.2 75 23 BFBZn KF DMAC 120/136 1/2 31.0 20.16/0.06 7.84/0.12 0.1/1.7 50 24 CFB Zn KFDMAC 120/140 1/3 24.5 14.82/0.06 7.84/0.12 0.1/1.7 50 BFB 1.95/0.006 25CFB Zn KF DMAC 60/140 1/3 27.0 14.82/0.06 7.84/0.12 0.1/1.7 50 26 CFB ZnKCl DMAC 120/135 2/2 33.18 29.64/0.12 15.68/0.24 0.2/2.7 75 27 CFB Zn BrDMAC 120/132 2/2 35.55 29.64/0.12 15.68/0.24 0.2/1.7 75 28 CFB Zn KIDMAC 120/126 2/2 32.7 29.64/0.12 15.68/0.24 0.5/3.0 75 29 BFB Zn KI DMAC120/136 1/2 32.0 20.16/0.06 7.84/0.12 0.1/0.6 50 30 CFB Zn KI DMF120/131 1/3 23.8 14.82/0.06 7.84/0.12 0.1/0.6 150  31 CFB Zn KI DMAC60/140 1/3 30.5 14.82/0.06 7.84/0.12 0.1/0.6 50 32 CFB Zn KI DMAC 80/1001/5 26.7 14.82/0.06 7.84/0.12 0.1/0.6 50 33 CFB Zn KI DMAC 100/120 1/529.2 14.82/0.06 7.84/0.12 0.1/0.6 50 34 CFB Zn K₂CO₃ DMAC 120/134 2/229.5 29.64/0.12 15.68/0.24 0.2/1.45 75 35 CFB Zn K₂SO₄ DMAC 120/134 2/232.6 29.64/0.12 15.68/0.24 0.2/1.15 75 36 CFB Zn KH₂PO₃ DMAC 120/140 1/236.2 14.82/0.06 7.84/0.12 0.1/0.83 50 37 CFB Zn K₂S₂O₈ DMAC 120/136 2/333.3 29.64/0.12 15.68/0.24 0.2/0.74 75 38 CFB Zn CH₃COOK DMAC 120/1351/3 28.1 14.82/0.06 7.84/0.12 0.3/3.1 50 39 CFB Zn KHP DMAC 120/136 1/327.9 14.82/0.06 7.84/0.12 0.1/0.5 50 40 CFB Zn NaCl DMAC 120/138 2/134.12 29.64/0.12 15.68/0.24 0.5/8.5 75 41 CFB Zn NaI DMAC 120/135 2/235.55 29.64/0.12 15.68/0.24 0.2/1.3 75 42 CFB Zn Na₂CO₃ DMAC 120/134 2/235.7 29.64/0.12 15.68/0.24 0.2/1.9 75 43 CFB Zn Na₂O DMAC 120/135 1/332.4 14.82/0.06 7.84/0.12 0.1/1.6 50 44 CFB Zn Na₂O₂ DMAC 120/136 1/337.3 14.82/0.06 7.84/0.12 0.3/3.85 50 45 CFB Zn C₂H₅ONa DMAC 120/136 1/325.8 14.82/0.06 7.84/0.12 0.3/4.4 50 46 CFB Zn CH₃COONa DMAC 120/135 1/333.3 14.82/0.06 7.84/0.12 0.3/3.66 50 47 CFB Zn C₆H₅COONa DMAC 120/1361/3 29.5 14.82/0.06 7.84/0.12 0.3/2.1 50 48 CFB Zn CH₃ONa DMAC 120/1361/3 33.8 14.82/0.06 7.84/0.12 0.3/5.6 50 49 CFB Zn CsF DMAC 120/140 1/229.52 14.82/0.06 7.84/0.12 0.1/0.66 50 50 CFB Zn MgCl₂ DMAC 120/130 2/231.9 29.64/0.12 15.68/0.24 0.2/2.1 75 51 CFB Zn MgSO₄ DMAC 120/132 2/238.39 29.64/0.12 15.68/0.24 0.2/1.7 75 52 CFB Zn MgCO₃ DMAC 120/132 1/233.8 14.82/0.06 7.84/0.12 0.1/1.2 50 53 BFB Zn CaCl₂ DMAC 120/136 1/232.8 20.16/0.06 7.84/0.12 0.1/0.9 50 54 CFB Zn CaCl₂ DMAC 120/140 1/331.4 14.82/0.06 7.84/0.12 0.1/0.9 50 BFB 1.95/0.006 55 CFB Zn CaCl₂ DMAC60/140 1/3 28.4 14.82/0.06 7.84/0.12 0.1/0.9 50 56 CFB Zn CaCO₃ DMAC120/134 2/2 32.85 29.64/0.12 15.68/0.24 0.2/2.0 75 57 CFB Zn CaSO₄ DMAC120/132 1/2 29.5 14.82/0.06 7.84/0.12 0.1/0.74 50 58 CFB Zn CaO DMAC120/140 1/3 35.24 14.82/0.06 7.84/0.12 0.1/1.8 50 59 CFB Zn Ca(OH)₂ DMAC120/130 1/2 23.14 14.82/0.06 7.84/0.12 0.3/4.0 50 60 CFB Zn Ba(NO₃)₂DMAC 120/136 1/3 29.52 14.82/0.06 7.84/0.12 0.1/0.38 50 61 CFB Zn BaCl₂DMAC 120/140 1/2 34.28 14.82/0.06 7.84/0.12 0.1/0.48 50 62 CFB ZnFeCl₃•6H₂O DMAC 120/136 1/3 25.3 14.82/0.06 7.84/0.12 0.1/0.37 50 63 CFBZn Fe(NO₃)₃•9H₂O DMAC 120/136 1/2 20.0 14.82/0.06 7.84/0.12 0.1/0.25 5064 CFB Zn CoCl₂•6H₂O DMAC 120/140 1/2 28.6 14.82/0.06 7.84/0.12 0.1/0.4250 65 CFB Zn Co(NO₃)₂•6H₂O DMAC 120/140 1/3 17.8 14.82/0.06 7.84/0.120.1/0.344 50 66 CFB Zn NiCl₂ DMAC 120/140 1/3 10.86 14.82/0.06 7.84/0.120.1/0.77 50 67 CFB Zn Ni(CH₃COO)₂•4H₂O DMAC 120/140 2/3 18.1 29.64/0.1215.68/0.24 0.2/0.8 75 68 CFB Zn NiCO₃ DMAC 120/140 1/2 26.7 14.82/0.067.84/0.12 0.1/0.84 50 69 CFB Zn Ni—Al—Si DMAC 120/140 1/2 36.614.82/0.06 7.84/0.12 0.5/ 50 70 CFB Zn Ni(NO₃)₂•6H₂O DMAC 120/140 1/313.8 14.82/0.06 7.84/0.12 0.1/0.34 50 71 CFB Zn CuCl₂•2H₂O DMAC 120/1401/3 24.5 14.82/0.06 7.84/0.12 0.1/0.59 50 72 CFB Zn CuSO₄•5H₂O DMAC120/134 1/2 15.8 14.82/0.06 7.84/0.12 0.1/0.4 50 73 CFB ZnCu(NO₃)₂•2.5H₂O DMAC 120/140 1/3 30.96 14.82/0.06 7.84/0.12 0.1/0.43 5074 CFB Zn ZnCl₂ DMAC 120/134 1/2 25.7 14.82/0.06 7.84/0.12 0.5/3.7 50 75CFB Zn ZnSO₄ DMAC 120/132 1/2 24.8 14.82/0.06 7.84/0.12 0.2/1.24 50 76CFB Zn Zn(NO₃)₂•6H₂O DMAC 120/132 1/2 30.8 14.82/0.06 7.84/0.12 0.2/0.6850 77 CFB Zn Zn(CH₃COO)₂•2H₂O DMAC 120/136 1/3 25.7 14.82/0.06 7.84/0.120.1/0.46 50 78 CFB Zn Ag₂SO₄ DMAC 120/134 1/2 23.8 14.82/0.06 7.84/0.120.1/0.32 50 79 CFB Zn Al(NO₃)₃•9H₂O DMAC 120/140 1/2 22.3 14.82/0.067.84/0.12 0.2/0.53 50 80 CFB Zn SnCl₂ DMAC 120/140 2/3 20.5 29.64/0.1215.68/0.24 0.2/1.0 75 81 CFB Zn Pb(NO₃)₂ DMAC 120/130 2/2 26.229.64/0.12 15.68/0.24 0.33/1.0 75 82 CFB Zn PbO DMAC 120/140 2/2 38.129.64/0.12 15.68/0.24 0.2/0.9 75 83 CFB Zn Pb₃O₄ DMAC 120/136 1/2 32.114.82/0.06 7.84/0.12 0.1/0.15 50 84 CFB Zn (NH₄)₂SiF₆ DMAC 120/140 1/333.6 14.82/0.06 7.84/0.12 0.1/0.56 50 85 CFB Zn P₂O₅ DMAC 120/140 1/233.5 14.82/0.06 7.84/0.12 0.1/0.66 50 86 CFB Zn H₃BO₃ DMAC 120/130 1/332.4 14.82/0.06 7.84/0.12 0.1/1.6 50 87 CFB Zn PTC-A₂ DMAC 120/140 2/335.7 29.64/0.12 15.68/0.24 0.43/2.5 75 88 CFB Zn PTC-A₃ DMAC 120/134 2/223.8 29.64/0.12 15.68/0.24 0.3/1.4 75 89 CFB Zn PTC-B₁ DMAC 120/135 2/337.91 29.64/0.12 15.68/0.24 0.5/1.2 75 90 CFB Zn 12-crown-4 DMAC 120/1401/3 32.4 14.82/0.06 7.84/0.12 0.3/1.7 50 91 CFB Zn 15-crown-5 DMAC120/140 1/3 35.2 14.82/0.06 7.84/0.12 0.3/1.36 50 92 CFB Zn NaNH₂ DMAC120/135 1/3 32.95 14.82/0.06 7.84/0.12 0.3/7.7 50 93 CFB ZnC₆H₄(OH)COONa DMAC 120/135 1/3 27.6 14.82/0.06 7.84/0.12 0.3/1.9 50 94CFB Zn C₄H₉KO DMAC 120/135 1/3 28.6 14.82/0.06 7.84/0.12 0.3/2.7 50 95CFB Zn C₃H₃KO₂ DMAC 120/137 1/3 31.6 14.82/0.06 7.84/0.12 0.3/2.7 50 96CFB Zn C₂Na₂O₄ DMAC 120/137 1/3 32.67 14.82/0.06 7.84/0.12 0.3/2.24 5097 CFB Zn C₈H₄KNO₂ DMAC 120/137 1/3 27.9 14.82/0.06 7.84/0.12 0.3/1.6250 98 CFB Zn I₂ DMAC 120/136 1/3 31.7 14.82/0.06 7.84/0.12 0.3/1.18 5099 CFB Zn Br₂ DMAC 120/134 1/3 37.0 14.82/0.06 7.84/0.12 0.3/1.88 50 100CFB Zn HCl (36%) DMAC 120/134 1/3 18.67 14.82/0.06 7.84/0.12 0.5/5 50Comparative CFB Zn none DMAC 120/130 2/26 34.5 example 1 59.28/0.2431.36/0.48 100  Comparative CFB Al KI DMAC 120/138 1/3 11.8 example 214.82/0.06 3.24/0.12 0.1/0.6 50 Comparative CFB Zn KI AN 80/82.5 1/2010.05 example 3 14.82/0.06 7.84/0.12 0.1/0.6 150  Note: someabbreviation chemical name is as follows PTC-A₁ Tetramethyl ammoniumchloride PTC-A₂ Phenyl trimethyl ammonium chloride PTC-A₃ Benzyltriethyl ammonium hydroxide PTC-B₁ Tetraphenylphosphonium bromide PTC-B₂Methyl triphenylphosphonium bromide KHP Potassium hydrogen phthalate CFB1,4-bis(chlorodifluoromethyl)Benzene BFB1,4-bis(bromodifluoromethyl)Benzene DMAC N,N-Dimethylacetamide DMFN,N-Dimethylformamide DMSO Dimethylsulfoxide AN Acetonitrile C₄H₉KOPotassium tert-butoxide C₃H₃KO₂ Potassium acrylate C₂Na₂O₄ Sodiumoxalate C₈H₄KNO₂ Potassium phthalimide K₂S₂O₈ Potassium persulfateNi—Al—Si Nickel-Nickel Oxide deposited on silica-Alumina XERTEXDohrmann(German company) product for GC packing column usage

TABLE 2 The parylene AF4 preparation accelerated by UV withphoto-initiator

Reaction parylene Reactant Reducing Solvent temperature Reaction AF4 (R)agent (RA) UV & initiator (P) (S) (° C.) time (hr) yield Embodiment(g/mol) (g/mol) (g/mmol) (ml) Initial/End Feed/End (%) 101 CFB Zn UVDMAC 120/134 1/20 33.9 14.82/0.06 7.84/0.12 50 102 CFB Zn UV + AIBN DMAC120/132 1/3 33.3 14.82/0.06 7.84/0.12 0.3/1.83 50 103 CFB Zn UV + HMPPDMAC 120/136 1/7 37.7 14.82/0.06 7.84/0.12 0.3/1.83 50 104 CFB Zn UV +HCPK DMAC 120/135 1/5 32.4 14.82/0.06 7.84/0.12 0.3/1.47 50 105 CFB ZnUV + BDK DMAC 120/140 1/4 29.5 14.82/0.06 7.84/0.12 0.3/1.17 50 106 CFBZn UV + BPO DMAC 120/140 1/4 27.7 14.82/0.06 7.84/0.12 0.3/1.24 50 107CFB Zn UV + DTBPO DMAC 120/136 1/4 24.8 14.82/0.06 7.84/0.12 0.3/0.86 50108 CFB Zn UV + MPMPO DMAC 120/136 1/4 36.2 14.82/0.06 7.84/0.120.3/1.07 50 109 CFB Zn UV + EAQ DMAC 120/138 1/4 36.6 14.82/0.067.84/0.12 0.3/1.27 50 110 BFB Zn UV + HMPP DMAC 120/136 1/3 36.520.16/0.06 7.84/0.12 0.3/1.83 50 111 CFB Zn UV + HMPP DMSO 120/136 1/425.7 14.82/0.06 7.84/0.12 0.3/1.83 50 112 CFB Zn UV + HMPP DMAC 60/1331/3 29.1 14.82/0.06 7.84/0.12 0.3/1.83 50 113 CFB Zn UV + HMPP DMAC120/136 1/3 27.6 14.82/0.06 7.84/0.12 0.3/1.83 150  114 CFB Zn UV + HMPPDMAC 120/135 1/2 30.0 14.82/0.06 15.68/0.24 0.3/1.83 50 115 CFB Zn UV +HMPP DMAC 120/134 1/4 30.5 14.82/0.06 7.84/0.12 1.0/6.1 50 ComparativeCFB Zn UV DMAC 120/130 2/20 35.7 example 4 29.64/0.12 15.68/0.24 100 Note: The above chemical name is as follows. AIBN2,2-azobisisobutyronitrile HMPP 2-hydroxy-2-methyl-1-phenyl-1-propanoneHCPK 1-hydroxy-cyclohexyl-phenyl ketone BDK benzyl α,α-dimethyl ketalBPO benzoyl peroxide DTBPO diphenyl-(2,4,6-trimethylbenzoyl)phosphineoxide EAQ 2-ethylanthraquinone MPMPO2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one

Although the present invention has been explained in relation to itspreferred embodiment, it is understood that many other possiblemodifications and variations can be made without departing from thespirit and scope of the invention as hereinafter claimed.

What is claimed is:
 1. A method of preparing parylene AF4(octafluoro-[2,2]-paracyclophane), which comprises the steps of: (A)providing a reactant, a reducing agent, and a catalyst, wherein thereactant is at least one selected from the group consisting of1,4-bis(chlorodifluoromethyl)benzene,1,4-bis(bromodifluoromethyl)benzene, and1,4-bis(iododifluoromethyl)benzene; the reducing agent is at least oneselected from the group consisting of zinc, nickel, lead, aluminum,copper, magnesium and tin; and the catalyst is at least one selectedfrom the group consisting of an alkali earth metal salt, an alkali earthmetal oxide, an alkali earth metal hydroxide; an amphoteric elementsalt, an amphoteric element oxide, an amphoteric element hydroxide, anamphoteric element peroxide, an amphoteric element salt containinghydrate; a non-metallic element acid, a non-metallic element oxide; ahalogen; a phase transfer catalyst of quaternary ammonium salt, a phasetransfer catalyst of quaternary phosphonium salt, and a phase transfercatalyst of crown ether; (B) forming a mixture by adding the reactant,the reducing agent, and the catalyst into an aprotic polar solvent; and(C) heating the mixture to obtain the parylene AF4.
 2. The methodaccording to claim 1, wherein the aprotic polar solvent in step (B) isat least one selected from the group consisting ofN,N-dimethylacetamide, dimethylsulfoxide, dimethylformamide,tetrahydrofurane, N-methylpyrrolidone, and acetonitrile.
 3. The methodaccording to claim 1, wherein the alkali earth salt in step (B) is atleast one selected from the group consisting of alkali earth metalhalide salt, alkali earth metal sulfate, alkali earth metal carbonate,and alkali earth metal nitrate.
 4. The method according to claim 1,wherein the amphoteric element salt in step (B) is at least one selectedfrom the group consisting of amphoteric element halide salt, amphotericelement sulfate, and amphoteric element nitrate.
 5. The method accordingto claim 1, wherein the non-metallic element acid in step (B) isselected boric acid.
 6. The method according to claim 1, wherein thenon-metallic element oxide in step (B) is selected phosphorus pentoxide.7. The method according to claim 1, wherein the halogen is at least oneselected from the group consisting of bromine and iodine.
 8. The methodaccording to claim 1, wherein the phase transfer catalyst of quaternaryammonium salt in step (B) is at least one selected from the groupconsisting of tetramethyl ammonium chloride, phenyl trimethyl ammoniumchloride, and benzyl triethyl ammonium chloride.
 9. The method accordingto claim 1, wherein the phase transfer catalyst of quaternaryphosphonium salt in step (B) is at least one selected from the groupconsisting of tetraphenyl phosphonium bromide, and methyl triphenylphosphonium bromide.
 10. The method according to claim 1, wherein thephase transfer catalyst of crown ether in step (B) is at least oneselected from the group consisting of 18-crown-6-ether,12-crown-4-ether, and 15-crown-5-ether.
 11. The method according toclaim 1, in step (B), wherein the weight ratio of the reducing agent tothe reactant is 1:1˜5.
 12. The method according to claim 1, in step (B),wherein the weight ratio of the reactant to the solvent is 1:1˜30. 13.The method according to claim 1, in step (B), wherein the weight ratioof the catalyst to the reactant is 1:10˜500.
 14. The method according toclaim 1, in step (C), wherein the reacting temperature is 50˜250° C.